Optimisation and validation of a HS-SPME-GC-IT/MS method for analysis of carbonyl volatile compounds as biomarkers in human urine: Application in a pilot study to discriminate individuals with smoking habits

被引:44
作者
Calejo, Isabel [1 ]
Moreira, Nathalie [1 ,2 ]
Araujo, Ana Margarida [1 ]
Carvalho, Marcia [1 ,3 ]
Bastos, Maria de Lourdes [1 ]
de Pinho, Paula Guedes [1 ]
机构
[1] Univ Porto, Fac Pharm, Dept Biol Sci, UCIBIO REQUIMTE,Lab Toxicol, P-4050313 Porto, Portugal
[2] Portuguese Catholic Univ, Sch Biotechnol, CBQF Ctr Biotechnol & Fine Chem, P-4202401 Porto, Portugal
[3] Univ Fernando Pessoa, FP ENAS, CEBIMED, Fundacao Ensino & Cultura Fernando Pessoa, Porto, Portugal
关键词
HS-SPME-GC-IT/MS method; Central Composite Design (CCD); Carbonyl compounds; Urinary biomarkers; Smoking habits; SOLID-PHASE MICROEXTRACTION; CHROMATOGRAPHY-MASS SPECTROMETRY; GAS-CHROMATOGRAPHY; ORGANIC-COMPOUNDS; QUANTITATIVE-ANALYSIS; OXIDATIVE STRESS; POSSIBLE MARKERS; EXHALED BREATH; ALDEHYDES; HEADSPACE;
D O I
10.1016/j.talanta.2015.09.070
中图分类号
O65 [分析化学];
学科分类号
070302 ; 081704 ;
摘要
A new and simple analytical approach consisting of an automated headspace solid-phase microextraction (HS-SPME) sampler coupled to gas chromatography-ion trap/mass spectrometry detection (GC-IT/MS) with a prior derivatization step with O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine hydrochloride (PFBHA) was developed to detect volatile carbonyl metabolites with low molecular weights in human urine. A central composite design (CCD) was used to optimise the PFBHA concentration and extraction conditions that affect the efficiency of the SPME procedure. With a sample volume of 1 mL, optimal conditions were achieved by adding 300 mg/L of PFBHA and allowing the sample to equilibrate for 6 min at 62 degrees C and then extracting the samples for 51 min at the same temperature, using a divinylbenzene/polydimethylsiloxane (DVB/PDMS) fibre. The method allowed the simultaneous identification and quantification of 44 carbonyl compounds consisting of aldehydes, dialdehydes, heterocyclic aldehydes and ketones. The method was validated with regards to the linearity, inter- and intra-day precision and accuracy. The detection limits ranged from 0.009 to 0.942 ng/mL, except for 4-hydroxy-2-nonenal (15 ng/mL), and the quantification limits varied from 0.029 to 1.66 ng/mL, except for butanal (2.78 ng/mL), 2-butanone (2.67 ng/mL), 4-heptanone (3.14 ng/mL) and 4-hydroxy-2-nonenal (50.0 ng/mL). The method accuracy was satisfactory, with recoveries ranging from 90 to 107%. The proof of applicability of the methodology was performed in a pilot target analysis of urine samples obtained from 18 healthy smokers and 18 healthy non-smokers (control group). Chemometric supervised analysis was performed using the volatile patterns acquired for these samples and clearly showed the potential of the volatile carbonyl profiles to discriminate urine from smoker and non-smoker subjects. 5-Methyl-2-furfural (p<0.0001), 2-methylpropanal, nonanal and 2-methylbutanal (p < 0.05) were identified as potentially useful biomarkers to identify smoking habits. (C) 2015 Elsevier B.V. All rights reserved.
引用
收藏
页码:486 / 493
页数:8
相关论文
共 57 条
[1]   An investigation of volatile organic compounds from the saliva of healthy individuals using headspace-trap/GC-MS [J].
AL-Kateb, Huda ;
Costello, Benjamin de Lacy ;
Ratcliffe, Norman .
JOURNAL OF BREATH RESEARCH, 2013, 7 (03)
[2]  
Anton A. P., 2014, J CHROMATOGR A
[3]   Development and validation of automatic HS-SPME with a gas chromatography-ion trap/mass spectrometry method for analysis of volatiles in wines [J].
Barros, Elisabete Paula ;
Moreira, Nathalie ;
Pereira, Giuliano Elias ;
Ferreira Leite, Selma Gomes ;
Rezende, Claudia Moraes ;
de Pinho, Paula Guedes .
TALANTA, 2012, 101 :177-186
[4]  
Barros GP, 2012, INT J GEOPHYS, V2012, DOI [10.1155/2012/459497, 10.5402/2012/137289]
[5]   Quantitative analysis of exhaled carbonyl compounds distinguishes benign from malignant pulmonary disease [J].
Bousamra, Michael, II ;
Schumer, Erin ;
Li, Mingxiao ;
Knipp, Ralph J. ;
Nantz, Michael H. ;
van Berkel, Victor ;
Fu, Xiao-An .
JOURNAL OF THORACIC AND CARDIOVASCULAR SURGERY, 2014, 148 (03) :1074-1080
[6]   Screening of tropical fruit volatile compounds using solid-phase microextraction (SPME) fibers and internally cooled SPME fiber [J].
Carasek, Eduardo ;
Pawliszyn, Janusz .
JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY, 2006, 54 (23) :8688-8696
[7]   Volatile organic compounds in exhaled breath as a diagnostic tool for asthma in children [J].
Dallinga, J. W. ;
Robroeks, C. M. H. H. T. ;
van Berkel, J. J. B. N. ;
Moonen, E. J. C. ;
Godschalk, R. W. L. ;
Jobsis, Q. ;
Dompeling, E. ;
Wouters, E. F. M. ;
van Schooten, F. J. .
CLINICAL AND EXPERIMENTAL ALLERGY, 2010, 40 (01) :68-76
[8]   A review of recent studies on malondialdehyde as toxic molecule and biological marker of oxidative stress [J].
Del Rio, D ;
Stewart, AJ ;
Pellegrini, N .
NUTRITION METABOLISM AND CARDIOVASCULAR DISEASES, 2005, 15 (04) :316-328
[9]  
Deng C., 2011, J CHROMATOGR B, V808, P269
[10]   GAS-CHROMATOGRAPHIC ANALYSIS OF REACTIVE CARBONYL-COMPOUNDS FORMED FROM LIPIDS UPON UV-IRRADIATION [J].
DENNIS, KJ ;
SHIBAMOTO, T .
LIPIDS, 1990, 25 (08) :460-464